Page 1322 - Advanced Organic Chemistry Part B - Reactions & Synthesis

ketone enolates in 67–69 stereochemistry of, 339 1299
stereoselectivity of, 68–69 thermal reversibility of, 342–344
kinetic versus thermodynamic control, 64–65, 71 hydrocarbonylation Index
macrocyclization by in epothilone A palladium-catalyzed, 749–750
synthesis, 1224 hydroformylation, 368–387
mechanism, 64–65 hydrogenation, 759–760
Mukaiyama aldol reaction, 82–86 metathesis reactions, 761–766
stereoselectivity of, 65–78, 93–101 catalysts for, 762
polar substituent effects in, 97, 105 examples, 766
stereoselectivity of, 86–134 mechanism, 764
chelation effects in, 92–96, 102–105 oxidation
control by aldehyde, 87–101 allylic, 1116–1117
control by enolate, 101–108 dihydroxylation, 1074–1081
Felkin model for, 90 palladium-catalyzed, 709–712
Alkenes singlet oxygen, 1117–1124
addition of trifluoroacetic acid, 294 selenium dioxide, 1124–1126
addition reactions with hydrogen halides, oxymercuration, 294–298
290–293 ozonolysis, 1129–1131
carbocation rearrangements during, 291 examples, 1130
stereochemistry of, 291–293 palladium-catalyzed arylation, 715–724
allylic oxidation, 1116–1126 radicals addition, 959–966
chromium reagents, 1116–1117 allylic stannanes, 965
arylation allylic silanes, 965
Meerwein arylation, 1035 examples, 964–965
palladium-catalyzed, 715–720 mechanism, 960
aziridination of, 947 substituent effects, 960
carboalumination, 354–355 reactions with
[2+2]cycloaddition acylium ions, 881–883
examples, 543 carbenes, 906–908, 916–934
intramolecular, 540–541 selenenylation of, 308–310
photocycloadditions, 544–548 sulfenylation of, 307–310
with carbonyl compounds, 548–551 synthesis from
with ketenes, 539–542 alkynes by addition of organocopper
dihydroxylation, 1074–1081 reagents, 697
computational model for, 1078–1079 alkynes by partial hydrogenation, 387
co-oxidants for, 1076 amine oxides by thermal elimination, 597–598
enantioselective, 1076–1078 borane derivatives, stereoselective, 795–797
examples, 1080 carbonyl compounds by olefination reactions,
diimide, reduction by, 388–390 157–176, 750
examples, 389–390 carbonyl compounds by reductive coupling,
electrophilic cyclization of, 310–328 444–452
epoxidation, 1091–1103 vic-diols by reductive elimination, 458–460
computational model, 1092 -halo sulfones by Ramberg-Backlund
by dioxiranes, 1097–1103 reaction, 895–897
enantioselective by manganese diimines, 1088 ketones by Shapiro reaction, 454–456
by hydrogen peroxide, 1097 -silyl carbanions by peterson reaction,
hydroxy directing effect, 1093, 1095 171–174
by peroxycarboxylic acids, 1091–1096 sulfones by Julia reaction, 174–176
by peroxyimidic acids, 1095–1097 Wittig reaction, 157–164
torsional effect on, 1093 xanthates by thermal elimination, 603
fluorination of, 303–304 Alkylation
halogenation of, 298–301 of carbon nucleophiles, 21–31
hydration of, 293 enamines, 46–48
hydroalumination, 353–355 enantioselective, 41–45
hydroboration, 337–344 imine anions, 48–54
enantioselective, 347–351 intramolecular, 36–40
by halo boranes, 330 hydrazones, 53–55
metal catalyzed, 341–342 stereoselectivity, of, 24–29, 32–33
regioselectivity of, 337–338 tanderm with birch reduction, 437